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WO2003069961A1 - Electroluminescent iridium compounds with phosphinoalkoxides and phenylpyridines or phenylpyrimidines and devices made with such compounds - Google Patents

Electroluminescent iridium compounds with phosphinoalkoxides and phenylpyridines or phenylpyrimidines and devices made with such compounds Download PDF

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WO2003069961A1
WO2003069961A1 PCT/US2003/004149 US0304149W WO03069961A1 WO 2003069961 A1 WO2003069961 A1 WO 2003069961A1 US 0304149 W US0304149 W US 0304149W WO 03069961 A1 WO03069961 A1 WO 03069961A1
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arom
bis
compound
nmr
bromohydrin
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French (fr)
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Vladimir Grushin
Viacheslav Alexandrovich Petrov
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E.I. Du Pont De Nemours And Company
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Priority to JP2003568940A priority Critical patent/JP2005518081A/ja
Priority to CA002476193A priority patent/CA2476193A1/en
Priority to AU2003213015A priority patent/AU2003213015A1/en
Priority to KR10-2004-7012168A priority patent/KR20040089601A/ko
Priority to EP03709057A priority patent/EP1472909A1/en
Publication of WO2003069961A1 publication Critical patent/WO2003069961A1/en

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    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C07F15/004—Iridium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5004—Acyclic saturated phosphines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/505—Preparation; Separation; Purification; Stabilisation
    • C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
    • C07F9/5068—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure >P-Hal
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/917—Electroluminescent

Definitions

  • This invention relates to electroluminescent complexes of iridium(lll) with phenylpyridines or phenylpyrimidines, which additionally have a phosphinoalkoxide ligand. It also relates to electronic devices in which the active layer includes an electroluminescent Ir(lll) complex. Description of the Related Art
  • Organic electronic devices that emit light, such as light-emitting diodes that make up displays, are present in many different kinds of electronic equipment.
  • an organic active layer is sandwiched between two electrical contact layers. At least one of the electrical contact layers is light-transmitting so that light can pass through the electrical contact layer.
  • the organic active layer emits light through the light-transmitting electrical contact layer upon application of electricity across the electrical contact layers.
  • organic electroluminescent compounds As the active component in light-emitting diodes. Simple organic molecules such as anthracene, thiadiazole derivatives, and coumarin derivatives are known to show electroluminescence. Semiconductive conjugated polymers have also been used as electroluminescent components, as has been disclosed in, for example, Friend et al., U.S. Patent 5,247,190, Heeger et al., U.S. Patent 5,408,109, and Nakano et al., Published European Patent Application 443 861. Complexes of 8-hydroxyquinolate with trivalent metal ions, particularly aluminum, have been extensively used as electroluminescent components, as has been disclosed in, for example, Tang et al., U.S. Patent 5,552,678.
  • the present invention is directed to an iridium compound having the following Formula I: lrL a Lbu (I) where
  • L a and L D are alike or different and each of L a and L D has Formula II, shown in Figure 1 , wherein:
  • R 1 through R ⁇ are independently selected from hydrogen, deuterium, alkyl, alkoxy, halogen, nitro, cyano, fluoro, C n (H+F)2 n +l, OC n (H+F)2 n +l , and OCF2X, where n is an integer from 1 through 12, and X is H, CI, or Br, and
  • A is C or N, provided that when A is N, there is no R1 ; and L' is a bidentate phosphino alkoxide ligand having Formula III, shown in Figure 2, wherein: R9 can be the same or different at each occurrence and is selected from C m (H+F) 2n + ⁇ , C 6 (H+F)pY 5- p, R10 can be the same or different at each occurrence and is selected from H, F, and C n (H+F)2n+ ⁇ ; Y is C m (H+F) 2m+ ⁇ ; n is an integer from 1 through 12; m is 2 or 3; p is 0 or an integer from 1 through 5.
  • the present invention is directed to phosphinoalkanol precursor compounds from which the phosphinoalkoxide ligands are made.
  • the phosphinoalkanol compounds have Formula lll-H, shown in Figure 2, in which R 9 , R 1 0, Y, n, m, and p are as defined above for Formula III.
  • the present invention is directed to a process for making a phosphinoalkanolcompound.
  • the present invention is directed to an organic electronic device having at least one emitting layer comprising the above Ir(lll) compound, or combinations of the above- lr(l 11) compounds.
  • compound is intended to mean an electrically uncharged substance made up of molecules that further consist of atoms, wherein the atoms cannot be separated by physical means.
  • ligand is intended to mean a molecule, ion, or atom that is attached to the coordination sphere of a metallic ion.
  • complex when used as a noun, is intended to mean a compound having at least one metallic ion and at least one ligand.
  • group is intended to mean a part of a compound, such a substituent in an organic compound or a ligand in a complex.
  • adjacent to when used to refer to layers in a device, does not necessarily mean that one layer is immediately next to another layer.
  • adjacent R groups is used to refer to R groups that are next to each other in a chemical formula (i.e., R groups that are on atoms joined by a bond).
  • photoactive refers to any material that exhibits electroluminescence and/or photosensitivity.
  • (H+F) is intended to mean all combinations of hydrogen and fluorine, including completely hydrogenated, partially fluorinated or perfluorinated substituents.
  • Electroluminescence is generally measured in a diode structure, in which the material to be tested is sandwiched between two electrical contact layers and a voltage is applied. The light intensity and wavelength can be measured, for example, by a photodiode and a spectrograph, respectively.
  • the IUPAC numbering system is used throughout, where the groups from the Periodic Table are numbered from left to right as 1 through 18 (CRC Handbook of Chemistry and Physics, 81 st Edition, 2000). DESCRIPTION OF THE DRAWINGS Figure 1 shows Formula II for phenylpyridine and phenylpyrimidine ligands useful in the metal complex of the invention, and Formula ll-H for the ligand precursor compound.
  • Figure 2 shows Formula III for phosphinoalkanoxide ligands useful in the metal complex of the invention, and Formula lll-H for the ligand precursor compound.
  • Figure 3 shows Equation 1 for forming the ligand precursor compound, ll-H.
  • Figure 4 shows Equation 2 for forming the ligand precursor compound, lll-H.
  • Figure 5 shows Formulae IV and V for bridged- Ir dimers.
  • FIG. 6 is a schematic diagram of a light-emitting device (LED).
  • FIG. 7 is a schematic diagram of an LED testing apparatus. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • the Ir(lll) compounds of the invention have Formula I, as defined above.
  • the compounds are frequently referred to as bis-cyclometalated complexes.
  • the cyclometalated complexes of the invention are neutral and non-ionic, and can be sublimed intact. Thin films of these materials obtained via vacuum deposition exhibit good to excellent electroluminescent properties.
  • Two of the ligands in the Ir(lll) compounds of the invention are phenylpyridine or phenylpyrimidine ligands having Formula II, shown in Figure 1.
  • the R1 through R ⁇ groups of Formula II may be chosen from conventional substitutents for organic compounds, such as alkyl, alkoxy, halogen, nitro, and cyano groups, as well as fluoro, fluorinated alkyl and fluorinated alkoxy groups.
  • the groups can be partially or fully fluorinated (perfluorinated).
  • the precursor 2-phenylpyridines and 2-phenylpyrimidines, Formula ll-H in Figure 1 are prepared, in good to excellent yield, using the Suzuki coupling of the substituted 2-chloropyridine or 2-chloropyrimidine with arylboronic acid as described in O. Lohse, P.Thevenin, E. Waldvogel Synlett, 1999, 45-48. This reaction is illustrated for the pyridine derivative, where X and Y represent substituents, in Equation (1) shown in Figure 3.
  • t-Bu represents a tertiary butyl group
  • the third ligand in the Ir(lll) compounds of the invention is a phosphinoalkoxide.
  • the precursor phosphinoalkanol compounds having Formula lll-H, as shown in Figure 2 can be prepared using known procedures, such as, for example, the procedure reported in Inorg. Chem. 1985, v.24, p.3680, for 1 ,1-bis(trifluoromethyl)-2- (diphenylphosphino)ethanol. This method involves the reaction of diphenylphosphinomethyllithium with hexafluoroacetylacetone, followed by hydrolysis.
  • the phosphino alkanol compounds can be prepared using the reaction of 1 ,1-bis(trifluoromethyl)ethylene oxide with the corresponding secondary phosphine (R 9 2 PH) or its deprotonated form as a salt ([R 9 2P]M), where M is Li, Na, or K.
  • the deprotonated form can be prepared by the treatment of the secondary phosphine with a strong base, such as BuLi or t-BuOK.
  • the phosphino alkanol compounds can be made using dilithiated derivatives of halohydrins, which can be prepared as described in J. Chem. Soc, Perkin Trans. 1, 1983, p. 3019. The dilithio-derivative is reacted with a chlorophosphine to produce the desired phosphinoalkanol ligand.
  • a dried bromohydrin is combined with n-butyl lithium, wherein the molar ratio of n-butyl lithium to bromohydrin is about 2.
  • the preferred process for preparing the phosphino alkanol comprises the steps: (1) combining an epoxide with aqueous HBr, to form a bromohydrin;
  • step (3) combining the dried bromohydrin from step (2) with n-butyl lithium, wherein the molar ratio of n-butyl lithium to the bromohydrin is about 2; (4) adding a chlorophosphine to the product of step (3); and
  • the epoxide can be substituted with groups such as alkyl, partially fluorinated alkyl, and perfluoroalkyl groups; preferably trifluoromethyl groups.
  • the chlorophosphine is a chlorodialkylphosphine or a chlorodiarylphosphine; preferably, chlorodiphenylphosphine.
  • the acid can be any Bronsted acid which will provide a proton in the last reaction step, preferably trifluoroacetic acid.
  • the reaction scheme is illustrated using bis(trifluoromethyl)ethylene oxide in Equation (2), shown in Figure 4.
  • the dilithiation of the bromohydrin deriving from bis(trifluoromethyl)ethylene oxide can be done with 2 equivalents of BuLi within 0.5 h at -78 °C. This is different from the literature procedure (J. Chem. Soc, Perkin Trans. 1, 1983, p. 3019) which employs 1 equivalent of BuLi for 3 hours, followed by 1 equivalent of naphthyl lithium for 5 hours at -78 °C. • Napthyl lithium is not commercially available and is more expensive to make. The process of the invention is, in general, faster and uses readily available butyl lithium.
  • R9 is C ⁇ Fs or CeHpYs-p, where Y is CF 3 and p is 3 or 4.
  • R 10 is CF 3 and m is 2.
  • Suitable phosphinoalkanol compounds include:
  • the phosphinoalkoxide ligands from the above compounds are, respectively (abbreviations provided in brackets): 1 -diphenylphosphino-2-propoxide [dppO] 1 -bis(trifluoromethyl)-2-(diphenylphosphino)ethoxide [PO-1 ] 1 ,1 -bis(trifluoromethyl)-2-(bis(3'5'- ditrifluoromethylphenyl)phosphino)ethoxide [PO-2] 1 , 1 -bis(trifluoromethyl)-2-(bis(4'- trifluoromethylphenyl)phosphino)ethoxide [PO-3] 1 , 1 -bis(trifluoromethyl)-2- (bis(pentafluorophenyl)phosphino)ethoxide [PO-4]
  • the iridium complexes of the invention can be prepared by first preparing an intermediate iridium dimer with the phenylpyridine or phenypyrimidine ligand.
  • the dichloro bridged dimers having Formula IV can generally be prepared by reacting iridium trichloride hydrate with the 2-phenylpyridine or 2-phenylpyrimidine in a suitable solvent, such as 2-ethoxyethanol.
  • the iridium bridged dimers having Formula V can generally be prepared by reacting iridium trichloride hydrate with the 2-phenylpyridine or
  • the chloro dicyclometalated complexes can react, under biphasic or homogeneous conditions, with either the phosphinoalkanols in the presence of a base, such as NaOH, or salts of the phosphinoalkanols.
  • a base such as NaOH
  • salts of the phosphinoalkanols are used with the dichloro bridged dimers, and also when intermediates having Formula V are used, no additional base is required for the synthesis.
  • Examples of compounds having Formula I, where L a is the same as i are given in Table 2 below, where Rl through R ⁇ are as shown in Formula I, and A is C.
  • the present invention also relates to an electronic device comprising at least one photoactive layer positioned between two electrical contact layers, wherein the at least one layer of the device includes the iridium complex of the invention.
  • Devices frequently have additional hole transport and electron transport layers.
  • a typical structure is shown in Figure 1.
  • the device 100 has an anode layer 110 and a cathode layer 150. Adjacent to the anode is a layer 120 comprising hole transport material. Adjacent to the cathode is a layer 140 comprising an electron transport material. Between the hole transport layer and the electron transport layer is the photoactive layer 130. Layers 120, 130, and 140 are individually and collectively referred to as the active layers.
  • the photoactive layer 130 can be a light-emitting layer that is activated by an applied voltage (such as in a light-emitting diode or light-emitting electrochemical cell), a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector).
  • an applied voltage such as in a light-emitting diode or light-emitting electrochemical cell
  • a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage
  • photodetectors include photoconductive cells, photoresistors, photoswitches, phototransistors, and phototubes, and photovoltaic cells, as these terms are describe in Markus, John, Electronics and Nucleonics Dictionary, 470 and 476 (McGraw-Hill, Inc. 1966).
  • the iridium compounds of the invention are particularly useful as the photoactive material in layer 130, or as electron transport material in layer 140.
  • the iridium complexes of the invention are used as the light-emitting material in diodes. It has been found that in these applications, the compounds of the invention do not need to be in a solid matrix diluent in order to be effective.
  • a layer that is greater than 20% by weight iridium compound, based on the total weight of the layer, up to 100% iridium compound, can be used as the emitting layer. Additional materials can be present in the emitting layer with the iridium compound. For example, a fluorescent dye may be present to alter the color of emission. A diluent may also be added.
  • the diluent can be a polymeric material, such as poly(N-vinyl carbazole) and polysilane. It can also be a small molecule, such as 4,4'-N,N'-dicarbazole biphenyl or tertiary aromatic amines. When a diluent is used, the iridium compound is generally present in a small amount, usually less than 20% by weight, preferably less than 10% by weight, based on the total weight of the layer.
  • the iridium complexes may be present in more than one isomeric form, or mixtures of different complexes may be present. It will be understood that in the above discussion of OLEDs, the term "the iridium compound" is intended to encompass mixtures of compounds and/or isomers.
  • the HOMO (highest occupied molecular orbital) of the hole transport material should align with the work function of the anode
  • the LUMO (lowest un-occupied molecular orbital) of the electron transport material should align with the work function of the cathode.
  • Chemical compatibility and sublimation temp of the materials are also important considerations in selecting the electron and hole transport materials.
  • the other layers in the OLED can be made of any materials which are known to be useful in such layers.
  • the anode 110 is an electrode that is particularly efficient for injecting positive charge carriers. It can be made of, for example materials containing a metal, mixed metal, alloy, metal oxide or mixed-metal oxide, or it can be a conducting polymer. Suitable metals include the Group 11 metals, the metals in Groups 4, 5, and 6, and the Group 8-10 transition metals. If the anode is to be light-transmitting, mixed-metal oxides of Groups 12, 13 and 14 metals, such as indium-tin- oxide, are generally used.
  • the anode 110 may also comprise an organic material such as polyaniline as described in “Flexible light-emitting diodes made from soluble conducting polymer,” Nature vol. 357, pp 477-479 (11 June 1992). At least one of the anode and cathode should be at least partially transparent to allow the generated light to be observed.
  • hole transport materials for layer 120 have been summarized for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Both hole transporting molecules and polymers can be used. Commonly used hole transporting molecules are: N,N'-diphenyl-N,N'-bis(3-methylphenyl)- [1 ,r-biphenyl]-4,4'-diamine (“TPD”), 1,1-bis[(di-4-tolylamino) phenyljcyclohexane (“TAPC”), N,N'-bis(4-methylphenyl)-N,N'-bis(4- ethylphenylHI S.S'-dimethy biphenylj ⁇ '-diamine (“ETPD”), tetrakis-(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (“PDA”), a- phenyl
  • hole transporting polymers are polyvinylcarbazole, (phenylmethyl)polysilane, and polyaniline. It is also possible to obtain hole transporting polymers by doping hole transporting molecules such as those mentioned above into polymers such as polystyrene and polycarbonate.
  • electron transport materials for layer 140 include metal chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum ("Alq 3 "); phenanthroline-based compounds, such as 2,9-dimethyl-4,7- diphenyl-1,10-phenanthroline (“DDPA”) or 4,7-diphenyl-1,10- phenanthroline (“DPA”), and azole compounds such as 2-(4-biphenylyl)-5- (4-t-butylphenyl)-1 ,3,4-oxadiazole (“PBD”) and 3-(4-biphenylyl)-4-phenyl- 5-(4-t-butylphenyl)-1,2,4-triazole (“TAZ").
  • metal chelated oxinoid compounds such as tris(8-hydroxyquinolato)aluminum (“Alq 3 ")
  • phenanthroline-based compounds such as 2,9-dimethyl-4,7- diphenyl-1,10-phen
  • the cathode 150 is an electrode that is particularly efficient for injecting electrons or negative charge carriers.
  • the cathode can be any metal or nonmetal having a lower work function than the anode.
  • Materials for the cathode can be selected from alkali metals of Group 1 (e.g., Li, Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, including the rare earth elements and lanthanides, and the actinides. Materials such as aluminum, indium, calcium, barium, samarium and magnesium, as well as combinations, can be used.
  • Li-containing organometallic compounds can also be deposited between the organic layer and the cathode layer to lower the operating voltage.
  • a layer between the conductive polymer layer 120 and the active layer 130 to facilitate positive charge transport and/or band-gap matching of the layers, or to function as a protective layer.
  • additional layers between the active layer 130 and the cathode layer 150 to facilitate negative charge transport and/or band-gap matching between the layers, or to function as a protective layer.
  • Layers that are known in the art can be used.
  • any of the above-described layers can be made of two or more layers.
  • inorganic anode layer 110 may be surface treated to increase charge carrier transport efficiency.
  • the choice of materials for each of the component layers is preferably determined by balancing the goals of providing a device with high device efficiency.
  • each functional layer may be made up of more than one layer.
  • the device can be prepared by sequentially vapor depositing the individual layers on a suitable substrate.
  • Substrates such as glass and polymeric films can be used.
  • Conventional vapor deposition techniques can be used, such as thermal evaporation, chemical vapor deposition, and the like.
  • the organic layers can be coated from solutions or dispersions in suitable solvents, using any conventional coating technique.
  • the different layers will have the following range of thicknesses: anode 110, 500-5000A, preferably 1000-2000A; hole transport layer 120, 50-1 OO0A, preferably 200-800A; light-emitting layer 130, 10-1000 A, preferably 100-800A; electron transport layer 140, 50-1 OOOA, preferably 200-800A; cathode 150, 200-1 OOOOA, preferably 300-5000A.
  • the location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device, can be affected by the relative thickness of each layer.
  • the thickness of the electron-transport layer should be chosen so that the electron-hole recombination zone is in the light-emitting layer.
  • the desired ratio of layer thicknesses will depend on the exact nature of the materials used.
  • the efficiency of devices made with the iridium compounds of the invention can be further improved by optimizing the other layers in the device.
  • more efficient cathodes such as Ca, Ba or LiF can be used.
  • Shaped substrates and novel hole transport materials that result in a reduction in operating voltage or increase quantum efficiency are also applicable.
  • Additional layers can also be added to tailor the energy levels of the various layers and facilitate electroluminescence.
  • the iridium complexes of the invention are phosphorescent and photoluminescent and may be useful in applications other than OLEDs.
  • organometallic complexes of iridium have been used as oxygen sensitive indicators, as phosphorescent indicators in bioassays, and as catalysts.
  • This example illustrates the preparation of the 2-phenylpyridines and 2-phenylpyrimidines which are used to form the iridium compounds.
  • 2-(2',4'-dimethoxyphenyl)pyridine was prepared via Kumada coupling of 2-chloropyridine with 2,4-dimethoxyphenylmagnesium bromide in the presence of [(dppb)PdCI 2 ] catalyst, where dppb represents 1,4-bis(diphenylphosphino)butane).
  • This example illustrates the preparation of the precursor compound 1 , 1 -bis(trifluoromethyl)-2-bis(triphenylphosphino)-ethanol (PO-1 H).
  • the compound was made by two different methods.
  • Method a The phosphino alkanol was made according to the procedure in Inorg. Chem. (1985), 24(22), pp. 3680-7. Under nitrogen, 1 ,1- bis(trifluoromethyl)ethylene oxide (12 g, 0.066 mol) was added dropwise to a pre-cooled (10-15 °C) solution of diphenylphosphine (10g, 0.053 mol) in dry THF (50 mL). The reaction mixture was stirred at 25°C for 2 days, after which NMR analysis indicated > 90% conversion.
  • Method a Under nitrogen, a stirring solution of (3,5-(CF 3 ) 2 C 6 H 3 ) 2 PH (1.50 g; 3.27 mmol; prepared as described in: Casey, C. P. et al., J. Am. Chem. Soc.
  • Method b Under nitrogen, to a stirring solution of 1 ,1-bis(trifluoromethyl)-2- bromoethanol (0.91 g) in dry ether (20 mL) cooled to -78 °C, was added drop-wise 1.6 M n-BuLi in hexanes (Aldrich; 4.35 mL). After 1 h at -78 °C, (3,5-(CF 3 ) 2 C 6 H 3 ) 2 PCI (1.63 g; prepared as described in: Casalnuovo et al., US Patent 5175335) was added drop-wise, at vigorous stirring, to the resulting solution of the dilithiated derivative.
  • This example illustrates the formation of dichloro-bridged dinuclear bis- cyclometallated Ir complexes.
  • the Ir complexes were prepared by the reaction between lrCl 3 -nH 2 0 and the corresponding 2-arylpyridine in aqueous 2- ethoxyethanol.
  • the method is similar to the literatures procedure for 2- phenylpyridine (Sprouse, S.; King, K. A.; Spellane, P. J.; Watts, R. J., J. Am. Chem. Soc, 1984, 106, 6647-53; Garces, F. O.; King, K. A.; Watts, R. J., Inorg. Chem., 1988, 27, 3464-71.).
  • EXAMPLE 7 This example illustrates the formation of Ir complexes of the invention having the Formula I.
  • the general procedure was to combine a dichloro-bridged dinuclear bis-cyclometallated Ir complex from Example 6, a phosphinoalkanol compound (1.1-1.5 equivs per Ir), 1 ,2-dichloroethane (DCE; 3-12 mL), and 10% aqueous NaOH (2-10-fold excess) and stir under reflux (N 2 ) until all solids dissolved and then for additional 0.5-1.5 hours.
  • the products were isolated and purified in air.
  • the organic layer was separated, filtered through a short silica gel plug, and reduced in volume to 0.5-2 mL.
  • Compound 2-c (Table 2) A mixture of the dichloro-bridged dinuclear bis-cyclometallated Ir complex made with phenylpyridine compound 1-ah from Example 1 (200 mg), phosphinoalkanol PO-1 H from Example 2 (150 mg), DCE (5 mL), and 10% NaOH (1 mL) was vigorously stirred under reflux (N 2 ) for 0.5 h. The yellow organic layer (blue photoluminescent) was separated and filtered through a short silica plug. The aqueous layer was extracted with dichloromethane and passed through the same plug. The combined organic solutions were reduced in volume to 1-2 mL and treated with hexanes (10 mL; portionwise).
  • Compound 2-i (Table 2) A mixture of the dichloro-bridged dinuclear bis-cyclometallated Ir complex made with phenylpyridine compound 1-k (340 mg) from Example 1 , phosphinoalkanol PO-1 H from Example 2 (220 mg), DCE (5 mL), and 10% NaOH (1 mL) was vigorously stirred under reflux (N 2 ) for 20 min. The yellow organic layer (green photoluminescent) was separated and filtered through a short silica plug. The aqueous layer was extracted with dichloromethane and passed through the same plug. The combined organic solutions were reduced in volume to ca. 1 mL and treated with hexanes (10 mL). The yellow oil solidified upon trituration.
  • Compound 2-k (Table 2) A mixture of the dichloro-bridged dinuclear bis-cyclometallated Ir complex made with phenylpyridine compound 1-ai from Example 1 (300 mg), phosphinoalkanol PO-1 H from Example 2 (215 mg), DCE (5 mL), and 10% NaOH (2 mL) was vigorously stirred under reflux (N 2 ) for 2 h. The yellow organic layer (blue photoluminescent) was separated and filtered through a short silica plug. The aqueous layer was extracted with dichloromethane and passed through the same plug. The combined organic solutions were evaporated to dryness and treated with hexanes (10 mL).
  • EXAMPLE 8 This example illustrates the formation of an Ir complex of the invention having the Formula I, in a two-step, one-pot method, directly from lrCI 3 (hydrate).
  • Compound 2-f (Table 2)
  • EXAMPLE 9 This example illustrates the formation of OLEDs using the iridium complexes of the invention.
  • Thin film OLED devices including a hole transport layer (HT layer), electroluminescent layer (EL layer) and at least one electron transport layer (ET layer) were fabricated by the thermal evaporation technique.
  • An Edward Auto 306 evaporator with oil diffusion pump was used.
  • the base vacuum for all of the thin film deposition was in the range of 10"6 torr.
  • the deposition chamber was capable of depositing five different films without the need to break up the vacuum.
  • ITO indium tin oxide coated glass substrate
  • the substrate was first patterned by etching away the unwanted ITO area with 1 N HCI solution, to form a first electrode pattern.
  • Polyimide tape was used as the mask.
  • the patterned ITO substrates were then cleaned ultrasonically in aqueous detergent solution.
  • the substrates were then rinsed with distilled water, followed by isopropanol, and then degreased in toluene vapor for ⁇ 3 hours.
  • the cleaned, patterned ITO substrate was then loaded into the vacuum chamber and the chamber was pumped down to 10-6 torr. The substrate was then further cleaned using an oxygen plasma for about 5-10 minutes.
  • the OLED samples were characterized by measuring their (1) current- voltage (l-V) curves, (2) electroluminescence radiance versus voltage, and (3) electroluminescence spectra versus voltage.
  • the apparatus used, 200 is shown in Figure 7.
  • the l-V curves of an OLED sample, 220 were measured with a Keithley Source-Measurement Unit Model 237, 280.
  • the electroluminescence radiance (in the unit of Cd/m 2 ) vs. voltage was measured with a Minolta LS-110 luminescence meter, 210, while the voltage was scanned using the Keithley SMU.
  • the electroluminescence spectrum was obtained by collecting light using a pair of lenses, 230, through an electronic shutter, 240, dispersed through a spectrograph, 250, and then measured with a diode array detector, 260. All three measurements were performed at the same time and controlled by a computer, 270.
  • the efficiency of the device at certain voltage is determined by dividing the electroluminescence radiance of the LED by the current density needed to run the device. The unit is in Cd/A. The results are given in Table 6 below:

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JP2014231477A (ja) * 2011-09-21 2014-12-11 シャープ株式会社 アルコキシ基を有する遷移金属錯体、及びこれを用いた有機発光素子、色変換発光素子、光変換発光素子、有機レーザーダイオード発光素子、色素レーザー、表示装置、照明装置並びに電子機器
US10854826B2 (en) * 2014-10-08 2020-12-01 Universal Display Corporation Organic electroluminescent compounds, compositions and devices
US9397302B2 (en) * 2014-10-08 2016-07-19 Universal Display Corporation Organic electroluminescent materials and devices

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001041512A1 (en) * 1999-12-01 2001-06-07 The Trustees Of Princeton University Complexes of form l2mx as phosphorescent dopants for organic leds
US20010019782A1 (en) * 1999-12-27 2001-09-06 Tatsuya Igarashi Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex
WO2002002714A2 (en) * 2000-06-30 2002-01-10 E.I. Du Pont De Nemours And Company Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0725072A1 (de) * 1995-01-31 1996-08-07 Hoechst Aktiengesellschaft Verfahren zur Herstellung von Arylphosphinigsäurealkylestern
KR100913568B1 (ko) 1999-05-13 2009-08-26 더 트러스티즈 오브 프린스턴 유니버시티 전계인광에 기초한 고 효율의 유기 발광장치
KR100613674B1 (ko) 1999-05-14 2006-08-21 동경 엘렉트론 주식회사 웨이퍼 처리 장치 및 처리 방법
US6670645B2 (en) * 2000-06-30 2003-12-30 E. I. Du Pont De Nemours And Company Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds
JP4067286B2 (ja) * 2000-09-21 2008-03-26 富士フイルム株式会社 発光素子及びイリジウム錯体
US6963005B2 (en) * 2002-08-15 2005-11-08 E. I. Du Pont De Nemours And Company Compounds comprising phosphorus-containing metal complexes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001041512A1 (en) * 1999-12-01 2001-06-07 The Trustees Of Princeton University Complexes of form l2mx as phosphorescent dopants for organic leds
US20010019782A1 (en) * 1999-12-27 2001-09-06 Tatsuya Igarashi Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex
WO2002002714A2 (en) * 2000-06-30 2002-01-10 E.I. Du Pont De Nemours And Company Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BOERÉ, R.T. ET AL.: "Complexes of Hybrid Ligands. Synthesis of Fluoro-Alcohol Diarylphosphino Ligand and Its Complexes with Pt2+, Pd2+, Ni2+, Co2+, Cu+, and Rh 3+: Crystal and Molecular Structure of a Trans Square-Planar Ni2+ Complex with Two Bidentate Ligands Showing Cis-Trans Isomerism in Solution", INORGANIC CHEMISTRY, vol. 24, no. 22, 1985, pages 3680 - 3687, XP002243254 *
GRUSHIN V V ET AL: "Facile preparation and synthetic applications of LiCH2C(CF3)2OLi", JOURNAL OF FLUORINE CHEMISTRY, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 117, no. 2, 28 October 2002 (2002-10-28), pages 121 - 129, XP004389686, ISSN: 0022-1139 *
GRUSHIN V V ET AL: "New, efficient electroluminescent materials based on organometallic Ir complexes", CHEMICAL COMMUNICATIONS, ROYAL SOCIETY OF CHEMISTRY, GB, 2001, pages 1494 - 1495, XP002196401, ISSN: 1359-7345 *
MARSI, K.L.; CO-SARNO, M.E.: "Synthesis, Structure Analysis, and Stereochemistry of Some Reactions of cis- and trans-2,2,5-Trimethyl-3-phenyl-1,3-oxaphospholane", JOURNAL OF ORGANIC CHEMISTRY, vol. 42, no. 5, 1977, pages 778 - 781, XP002243253 *

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US7709100B2 (en) 2004-07-07 2010-05-04 Universal Display Corporation Electroluminescent efficiency
WO2006014599A3 (en) * 2004-07-07 2006-06-22 Universal Display Corp Stable and efficient electroluminescent materials
KR101258042B1 (ko) 2004-07-07 2013-04-24 유니버셜 디스플레이 코포레이션 안정하면서 효율이 높은 전기발광 재료
US20060163542A1 (en) * 2004-09-10 2006-07-27 Idemitsu Kosan Co., Ltd. Metal-complex compound and organic electroluminescence device using the compound
WO2006028224A1 (ja) * 2004-09-10 2006-03-16 Idemitsu Kosan Co., Ltd. 金属錯体化合物及びそれを用いた有機エレクトロルミネッセンス素子
JP2008532998A (ja) * 2005-03-05 2008-08-21 ドゥサン コーポレーション 新規イリジウム錯体及びこれを用いた有機電界発光素子
US7851072B2 (en) 2005-05-19 2010-12-14 Universal Display Corporation Stable and efficient electroluminescent materials
US8603645B2 (en) 2005-05-19 2013-12-10 Universal Display Corporation Stable and efficient electroluminescent materials
WO2007133523A3 (en) * 2006-05-08 2008-01-10 Du Pont Electroluminescent bis-cyclometalled iridium compounds and devices made with such compounds

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US7227041B2 (en) 2007-06-05
US20030173896A1 (en) 2003-09-18
US6919139B2 (en) 2005-07-19
EP1472909A1 (en) 2004-11-03
US20060057425A1 (en) 2006-03-16
US20050186447A1 (en) 2005-08-25
CN1656854A (zh) 2005-08-17
AU2003213015A1 (en) 2003-09-04
US7164045B2 (en) 2007-01-16
JP2005518081A (ja) 2005-06-16
KR20040089601A (ko) 2004-10-21
CA2476193A1 (en) 2003-08-21

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